WO1995020013A1 - Composition, film et moulage de resine biodegradable - Google Patents

Composition, film et moulage de resine biodegradable Download PDF

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Publication number
WO1995020013A1
WO1995020013A1 PCT/JP1995/000071 JP9500071W WO9520013A1 WO 1995020013 A1 WO1995020013 A1 WO 1995020013A1 JP 9500071 W JP9500071 W JP 9500071W WO 9520013 A1 WO9520013 A1 WO 9520013A1
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WO
WIPO (PCT)
Prior art keywords
biodegradable resin
resin composition
layered compound
inorganic layered
film
Prior art date
Application number
PCT/JP1995/000071
Other languages
English (en)
Japanese (ja)
Inventor
Kozo Kotani
Toshio Kawakita
Taiichi Sakaya
Toshiya Kuroda
Original Assignee
Sumitomo Chemical Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to US08/522,423 priority Critical patent/US6146750A/en
Priority to EP95906506A priority patent/EP0691381A4/fr
Publication of WO1995020013A1 publication Critical patent/WO1995020013A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/008—Additives improving gas barrier properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y10T428/1341—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
    • Y10T428/1383—Vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit is sandwiched between layers [continuous layer]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/251—Mica
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate

Definitions

  • the present invention relates to a resin composition excellent in both gas barrier properties and biodegradability, a film made of the resin composition, and a molded article.
  • Gas barrier films which are a type of functional film, have been widely put into practical use for preserving and protecting foods, pharmaceuticals, agricultural chemicals, cosmetics, and other contents where quality is an issue.
  • One of the most important of these uses is in the field of packaging.
  • the functions required for packaging that is, “wrapping things” or “materials” for packaging are diverse. Examples of such “packaging” functions include mechanical protection, safety, hygiene, workability, merchantability (transparency, printability, heat sealability), convenience, and economy.
  • various "gas barrier properties” which are one of the elements for preserving or protecting the contents, are important properties that affect the preservability of the above-mentioned contents such as foods. Distribution forms ⁇ With the diversification of packaging technology, stricter regulations on additives, and changes in tastes, the importance of this gas barrier property is increasing more and more. On the other hand, this “gas barrier property” has conventionally been a serious weakness of general plastic materials.
  • Gas barrier materials are mainly materials that effectively block oxygen.
  • the gasoline and lyre materials exhibit an oxygen blocking function, and are usually used to control various types of food deterioration. (Gas filling, vacuum packaging, etc.).
  • Such gas barrier materials include oxygen gas Barriers against various gases, organic solvent vapors, aromas, etc., or based on such functions as antibacterial, deodorant, sublimation prevention, etc., and also in the fields of carbon dioxide gas beverage containers, cosmetics, agricultural chemicals, medical treatment, etc. It is used very effectively.
  • thermoplastic resin oriented polypropylene, polyester, and polyamide films are widely used as packaging materials because of their excellent mechanical properties, heat resistance, and transparency. ing.
  • films made of these materials are used for food packaging, their oxygen permeability is insufficient due to their extremely high gas permeability, so that the contents may be deteriorated by oxidation or by the action of aerobic microorganisms. Deterioration of the target food is likely to occur. Therefore, when a film made of the above-mentioned material such as polypropylene is used for food packaging, usually, a method of laminating another film (or layer) having a good oxygen barrier property is often used.
  • the most typical means for forming such a film having good oxygen barrier properties include a method of laminating a metal foil such as aluminum or a method of evaporating the metal on the surface of a thermoplastic resin film. Therefore, the excellent gas barrier properties, particularly oxygen barrier properties, of the above metal foils are effectively utilized.
  • a transparent plastic material having low oxygen permeability for example, a film made of polyvinyl alcohol, a polyethylene / vinyl alcohol copolymer, and a polyvinylidene chloride resin has been conventionally known.
  • a film made of polyvinyl alcohol, a polyethylene / vinyl alcohol copolymer, and a polyvinylidene chloride resin has been conventionally known.
  • these plastic materials still have a property of permeating oxygen that cannot be ignored.
  • Japanese Unexamined Patent Publication No. Sho 62-1485332 discloses a coating comprising a transparent thermoplastic resin and a flaky my force having a particle size of 50 5zm or less and an aspect ratio of 5 or more. It describes a method for producing a gas barrier film in which a liquid composition is coated on a release substrate, dried, and then peeled off from the substrate.
  • 64-43554 discloses that flakes of muscovite (KA (AlSi 3 O 10 ) (OH) 2: non-swelling type of my force) are used as the flaky my force and the particle size is 325 mesh. (44 / m) and compositions for barrier layers using aspect ratios in the range of 20 to 140 are disclosed. Further, Japanese Patent Application Laid-Open No. 03-093542 discloses a coating containing a modified silyl group-containing polyvinyl alcohol and a synthetic hectrite (trade name: Laponite XLS, manufactured by Nippon Silica Kogyo KK) in a weight ratio of 50:50. A method for producing a barrier plastic film in which a composition is applied on biaxially stretched polyethylene terephthalate (OPET), dried, and then heat-treated (130 to 150 ° C) is disclosed.
  • OPET biaxially stretched polyethylene terephthalate
  • packaging materials are generally provided for “disposable” applications, it is becoming important to provide biodegradability to the packaging materials in accordance with the growing interest in global environmental issues in recent years.
  • An object of the present invention is to provide a resin composition, a film or a molded product that solves the above-mentioned problems, and more specifically, a resin having both good levels of oxygen barrier properties and biodegradability. It is to provide a composition, a film or a molded article. Disclosure of the invention
  • the present inventors have conducted intensive studies and found that combining a biodegradable resin with an inorganic layered compound having a specific aspect ratio to form a resin composition has not only excellent gas barrier properties but also excellent biodegradability. It has been found that a resin composition which also exerts the above effect is provided. As a result of further studies by the present inventors, the biodegradable resin film or molded article having at least one layer (or at least a part thereof) of such a specific resin composition has the above-mentioned excellent properties. Gasoline and biodegradability are substantially reduced I found nothing.
  • the biodegradable resin composition of the present invention is based on the above findings, and more specifically, comprises a biodegradable resin and an inorganic layered compound having an aspect ratio of 50 or more and 500 or less. It is a thing.
  • At least one layer (or portion) composed of a biodegradable resin composition containing a biodegradable resin and an inorganic layered compound having an aspect ratio of 50 or more and 500 or less is used.
  • the present invention provides a biodegradable resin film or a molded product in a part.
  • FIG. 1 is a graph schematically showing the relationship between the X-ray diffraction peak of an inorganic layered compound and the “unit thickness a” of the compound.
  • FIG. 2 is a graph schematically showing the relationship between the X-ray diffraction peak of a resin composition containing an inorganic layered compound and the “plane spacing d” of the composition.
  • FIG. 3 shows the X-ray diffraction peak of the resin composition when the peak corresponding to “plane spacing d” overlaps the halo (or background) and is difficult to detect, and the “plane spacing d” of the composition.
  • 6 is a graph schematically showing the relationship with. In this figure, the area of the portion excluding the baseline on the lower angle side than 20 d is defined as the peak corresponding to the “surface distance d”.
  • FIG. 4 is a schematic cross-sectional view showing one embodiment of the biodegradable resin film of the present invention.
  • FIG. 5 is a schematic cross-sectional view showing another embodiment (laminated type) of the biodegradable resin film of the present invention.
  • FIG. 6 is a schematic sectional view showing still another embodiment of the biodegradable resin film (laminated type) of the present invention.
  • FIG. 7 (Table 1) is a table showing the configuration of the laminated films obtained in the examples, and data such as oxygen permeability.
  • Figure 8 shows the polyvinyl alcohol PVA used in the examples—117 H / Kunipia F 3 is a graph showing an X-ray diffraction peak of the composition.
  • FIG. 9 is a graph showing an X-ray diffraction peak of Kunipia F (montmorillonite) used in the examples.
  • FIG. 12 is a graph showing an X-ray diffraction peak (the pattern of FIG. 3 above) of a composition having a plane spacing d ⁇ 4 4 .13 angstroms.
  • FIG. 13 is a graph showing an X-ray diffraction peak (the pattern of FIG. 3 above) of a composition having a plane spacing d ⁇ 4 4 .13 ⁇ .
  • biodegradable resin constituting the biodegradable resin composition of the present invention
  • a known biodegradable (or biodegradable) resin bio-degradable resin
  • biodegradable resin refers to a resin having the property of being decomposable or degradable by the action of microorganisms.
  • the biodegradable resin composition, film, and molded product of the present invention have a biodegradable resin that is comparable to Biopol (trade name, poly-13-hydroxybutyrate manufactured by ICI, UK). It preferably has degradability.
  • the residual area ratio of poly (3-hydroxybutyrate) is defined as “B ′” and the residual area ratio of the sample composed of the biodegradable resin composition of the present invention is defined as “S”, Preferably, 0 ⁇ S ⁇ 90.
  • the residual area ratio 2 (film bottom area after the decomposition test) / (film bottom area before the decomposition test) is XI 00.
  • biodegradable resin a biopolymer synthesized in a living body (and a chemically modified product thereof) or a biodegradable synthetic polymer is preferably used. More specifically, for example, cellulose; cellulose derivatives such as hydroxymethylcellulose, hydroxyxethylcellulose, and carboxymethylcellulose; amylose, amylobectin, pullulan, curdlan, xanthan, chitin, chitosan, etc.
  • microbial polyesters such as poly-3-hydroxybutylate, 3-hydroxybutylate 3-hydroxypererate copolymer, biodegradable aliphatic polyesters, polyvinyl alcohol, Polyethylene One year, you can refer to the High Polymer Publishing Association).
  • the degree of “saponification” in the polyvinyl alcohol is preferably 70% or more, more preferably 85% or more in terms of mole percentage.
  • the degree of polymerization of the polyvinyl alcohol is preferably from 100 to 500 (more preferably, from 200 to 300).
  • the “polysaccharides and derivatives thereof” usable in the present invention also include biopolymers synthesized in a biological system by polycondensation of various monosaccharides, and those obtained by chemically modifying them.
  • Specific examples of such “polysaccharides and derivatives thereof” include, for example, cellulose; cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose; amylose, amylopectin, pullulan, curdlan, xanthan , Chitin, chitosan and the like.
  • “Layered compound” refers to a compound or substance having a layered structure.
  • the term “layered structure” refers to a structure in which planes in which atoms are strongly bonded by covalent bonds or the like and are densely arranged are stacked substantially parallel by weak bonding force such as van der Waalska.
  • the “inorganic layered compound” that can be used in the present invention is not particularly limited as long as the “factor ratio” measured by the method described below is 50 or more and 500 or less. From the viewpoint of gas barrier properties, the aspect ratio is preferably 100 or more (especially 200 or more).
  • the aspect ratio is less than 50, the gas barrier properties will not be sufficiently developed. On the other hand, it is technically difficult to obtain an inorganic layer compound Asupe transfected ratio exceeds 5 0 0 0, also in terms of c manufacturability to be expensive in terms of cost or economical, this ⁇ scan It is preferable that the impact ratio is 2000 or less (more preferably, 1500 or less). From the viewpoint of the balance between gas pallidability and manufacturability, this aspect ratio should be 200 to Enzymatically degradable synthetic polymers such as recall.
  • the biodegradable resin usable in the present invention is preferably a high hydrogen bonding resin from the viewpoint of gas barrier properties.
  • the “high hydrogen-bonding resin” has a weight percentage of hydrogen-bonding groups (when two or more hydrogen-bonding groups are present, the total thereof) of 10% or more (and further, (About 20% to 60%) is preferable.
  • hydrogen-bonding group refers to a group having at least one hydrogen atom directly bonded to an atom (hetero atom) other than carbon.
  • the hydrogen bonding group include a hydroxyl group (including a carboxyl group), an amino group, a thiol group, and an amide group.
  • the content of these hydrogen-bonding groups can be suitably measured, for example, by a nuclear magnetic resonance (NMR) technique such as H-NMR 13 C-NMR.
  • the high hydrogen bonding resin that can be used in the present invention is not particularly limited as long as it has the above-mentioned “high hydrogen bonding property”.
  • polyvinyl alcohol, polysaccharides, and derivatives thereof can be preferably used.
  • polyvinyl alcohol is a polymer having a monomer unit of vinyl alcohol as a main component.
  • examples of such “polyvinyl alcohol” include, for example, a polymer obtained by hydrolysis or ester exchange (saponification) of an acetate portion of a vinyl acetate polymer (more precisely, a copolymer of vinyl alcohol and vinyl acetate). And a polymer obtained by saponifying a vinyl trifluoroacetate polymer, a vinyl formate polymer, a vinyl vivalate polymer, a t-butyl vinyl ether polymer, a trimethylsilyl vinyl ether polymer, etc.
  • the “particle size” measured by the method described below is preferably the following. If the particle size exceeds 5 / zm, the film forming property or moldability of the resin composition tends to decrease.c From the viewpoint of the transparency of the resin composition, the particle size is 3 / m or less. It is even better. When the resin composition of the present invention is used for applications where transparency is important (for example, food packaging applications), it is particularly preferable that the particle size is 1 ⁇ m or less.
  • the inorganic layered compound used in the present invention is preferably one having low toxicity or almost no toxicity in the ecosystem.
  • examples of such an inorganic layered compound include a phosphate-based derivative type compound (zirconium phosphate-based compound and the like), a clay-based mineral, and the like.
  • An inorganic layered compound having a property of swelling and cleaving in a solvent is preferably used from the viewpoint of easily obtaining an extremely large aspect ratio (an aspect ratio of about 200 or more). .
  • the degree of the “swelling / cleaving” property of the inorganic layered compound used in the present invention in a solvent can be evaluated by the following “swelling / cleaving” test.
  • the swelling property of the inorganic layered compound is preferably about 5 or more (more preferably about 20 or more) in the following swelling test.
  • the cleavage property of the inorganic layered compound is preferably about 5 or more (more preferably about 20 or more) in the following cleavage test.
  • a solvent having a density lower than the density of the inorganic layered compound is used as the solvent.
  • the inorganic layered compound is a natural swellable clay mineral, it is preferable to use water as the solvent.
  • Clay-based minerals generally have a two-layer structure in which an octahedral layer with aluminum or magnesium as the central metal is provided above the tetrahedral layer of silica; and the tetrahedral layer of silica is formed of aluminum or magnesium. It is classified as a type having a three-layer structure in which the octahedral layer made of metal is narrowed from both sides.
  • the former two-layer structure type includes kaolinite group, antigorite group, and the like.
  • the latter three-layer structure type includes smectite group, vermiculite group, and my group according to the number of interlayer cations. Can be mentioned.
  • these clay-based minerals include kaolinite, date kitite, naklite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectrite, tetrasilyl mymai, sodium teniolite. , Muscovite, margarite, talc, vermiculite, phlogopite, zansophyllite, chlorite and the like.
  • the “particle size” of the inorganic layered compound is determined in a solvent by a dynamic light scattering method (photon correlation) as described later.
  • Method (L) the dynamic light scattering method is a particle-based measurement method using the scattering phenomenon of laser, and the scattered light from a group of particles performing Brownian motion, that is, the movement speed or particle diameter of the particles, Have dependent “fluctuations” This is a method of detecting scattered light and obtaining information on the particle size by calculation.
  • the particle size of the inorganic layered compound in the resin can be approximated by the “particle size in solvent” obtained by the dynamic light scattering method.
  • the particle size of the inorganic layered compound in the resin is determined by the dynamic light It can be sufficiently approximated by the “particle size in the solvent” obtained by the scattering method.
  • L is the particle size of the inorganic layered compound determined by the dynamic light scattering method described above in a solvent
  • a is the unit thickness of the inorganic layered compound.
  • the “unit thickness a” is a value determined based on the measurement of the inorganic layered compound alone by a powder X-ray diffraction method or the like described later. More specifically, as shown schematically in the graph of Fig. 1, where the horizontal axis is 26 and the vertical axis is the intensity of the X-ray diffraction peak, it corresponds to the lowest angle peak among the observed diffraction peaks.
  • the inorganic layered compound in the resin composition is It is possible to find the surface distance d c
  • the diffraction peak position corresponding to the above “unit thickness a” is shown. Therefore, among the diffraction peaks observed on the low angle (large interval) side, the interval corresponding to the peak on the lowest angle side is defined as “plane interval d” (a d). As schematically shown in the graph of Fig. 3, the peak corresponding to the above-mentioned "surface distance d" is a halo (or background).
  • the area of the portion excluding the base line on the lower angle side than 2 S d is defined as the peak corresponding to the “surface distance d”.
  • “6> d ” is the diffraction angle corresponding to “(unit length a) + (width of single resin chain)”.
  • the “integrated intensity” of the diffraction peak (corresponding to the plane distance d) observed in the powder X-ray diffraction of the resin composition is different from the integral intensity of the reference diffraction peak (corresponding to “plane distance a”).
  • the relative ratio is preferably 2 or more (more preferably 10 or more).
  • Equal to or greater than the width of the chain (k (d-a) width of one resin chain).
  • Such a “width of a single resin chain” can be obtained by simulation calculation or the like.
  • a ⁇ d between the plane distance d obtained by the powder X-ray diffraction method of the resin composition and the ⁇ unit thickness a '' obtained by the powder X-ray diffraction measurement of the inorganic layered compound alone.
  • the definition Z of the aspect ratio used in the present invention has sufficient validity.
  • the term “aspect ratio” or “particle size” means “aspect ratio Z” defined above or “particle size L determined by dynamic light scattering method”.
  • the solvent that swells the above-mentioned inorganic layered compound is not particularly limited as long as it is a solvent that can be used for producing a resin composition.
  • the solvent may be water; alcohols such as methanol; polar solvents such as dimethylformamide, dimethylsulfoxide and acetone; or two of these solvents. Examples thereof include the above mixtures. From the viewpoint of easy removal after forming or forming the resin composition, it is preferable to use alcohols such as water and methanol having a relatively low boiling point.
  • the hydrogen-bonding resin may be used, if necessary, for the purpose of improving the water resistance (barrier properties after a water-resistant environment test) of the high hydrogen-bonding resin.
  • a base crosslinking agent may be used.
  • the crosslinking agent for a hydrogen bonding group that can be used in the present invention is not particularly limited.
  • the crosslinking agent include a titanium-based coupling agent, a silane-based coupling agent, a melamine-based coupling agent, an epoxy-based coupling agent, an isocyanate-based coupling agent, a copper compound, and a zirconia compound. From the viewpoint of improving water resistance, a zirconia compound is particularly preferably used.
  • zirconium compounds include, for example, zirconium halides such as zirconium oxychloride, zirconium hydroxychloride, zirconium tetrachloride and zirconium bromide; zirconium salts of mineral acids such as zirconium sulfate, basic zirconium sulfate and zirconium nitrate Organic zirconium salts such as zirconium formate, zirconium acetate, zirconium propionate, zirconium caprylate and zirconium stearate; ammonium zirconium carbonate, sodium zirconium sulfate, ammonium zirconium acetate, sodium zirconium oxalate; Zirconium complex salts such as sodium zirconium citrate and zirconium ammonium citrate; and the like.
  • zirconium halides such as zirconium oxychloride, zirconium hydroxychloride, zi
  • the resin composition, film or molded article of the present invention preferably has transparency from the viewpoint of convenience when used for applications such as packaging.
  • This transparency is preferably at least 80% (and more preferably at least 85%) in terms of total light transmittance at a wavelength of 500 nm.
  • Such transparency can be suitably measured by, for example, a commercially available spectrophotometer (manufactured by Hitachi, Ltd., self-recording spectrophotometer type 330).
  • the resin composition, film or molded article of the present invention has gas barrier properties.
  • the gas barrier property is preferably an oxygen permeability under a condition of 30 ° C. and 60 RH (relative humidity), and is preferably not more than 0.5 cc / m 2 ⁇ day ⁇ atm, more preferably 0.2 cc. / m 2 ⁇ day ⁇ atm or less (in particular 0. 1 5 cc / m 2 ⁇ day ⁇ atm or less) is preferably.
  • the method of blending or producing the composition comprising the above-mentioned inorganic layered compound and the biodegradable resin is not particularly limited. From the viewpoint of uniformity or ease of operation at the time of compounding, for example, a method in which a liquid in which a resin is dissolved and a dispersion in which an inorganic layered compound is swollen and cleaved in advance is mixed, and then the solvent is removed (No. Method 1); Method of adding a dispersion obtained by swelling and cleaving an inorganic layered compound to a resin and removing the solvent-1 (Method 2);
  • Method 3 A method in which a layered compound is added to form a swelled and cleaved dispersion and the solvent is removed (Method 3); a method in which a resin and an inorganic layered compound are kneaded by heat (Method 4); and the like can be used. From the viewpoint that a large aspect ratio of the inorganic layered compound can be easily obtained, the former three (methods 1 to 3) are preferably used.
  • the temperature is from 110 ° C to 220 ° C (furthermore, from 130 ° C to 210 ° C).
  • Heat aging at the following temperature is preferred from the viewpoint of improving the water resistance (barrier properties after a water resistance environment test) of the film.
  • the aging time is not particularly limited.In consideration of the fact that the film needs to reach at least the set temperature, for example, in the case of a heating medium contact type drying method such as a hot air dryer, the drying time is 1 second or more and 100 minutes. The following (more preferably, about 3 seconds to 10 minutes) is preferable from the viewpoint of the balance between water resistance and productivity.
  • the heat source for this aging is not particularly limited.
  • various methods such as hot roll contact, heat medium contact (air, oil, etc.), infrared heating, microwave heating, and the like can be applied.
  • the effect of improving the water resistance here is when the biodegradable resin is a particularly high hydrogen bonding resin, and / or when the inorganic layered compound is a clay mineral having swelling properties, Significantly higher when either one (or more preferably both) is satisfied.
  • the composition ratio (volume ratio) of the inorganic layered compound and the biodegradable resin used in the present invention is not particularly limited, but from the viewpoint of the balance between gas barrier properties and film forming properties (or moldability), inorganic layered compounds are preferred. /
  • the volume ratio of biodegradable resin (the ratio at the time of preparation) is in the range of 5/95 to 90/10, and the volume ratio is in the range of 5/95 to 50/50 (particularly, the volume ratio is 10/90 to 30/70).
  • volume ratio When the volume ratio is in the range of 5/95 to 30/70, it is advantageous in improving the flexibility as a film or a molded product. Further, when the volume ratio is in the range of 7/93 to 17/83, it is more advantageous in terms of suppressing a decrease in barrier property due to bending and increasing peel strength.
  • Such a volume ratio is obtained by dividing the values of the numerator (weight of the inorganic layered compound) and the denominator (weight of the biodegradable resin) of the weight ratio at the time of “feeding” these components by the respective densities. Can be calculated.
  • the density of a biodegradable resin for example, polyvinyl alcohol
  • the crystallinity of the biodegradable resin is It can be calculated assuming 50%.
  • volume ratio (volume fraction) of the above-mentioned inorganic layered compound / biodegradable resin is smaller than 5/95, the barrier performance tends to be insufficient.
  • volume ratio is more than 90/10, the film formability or formability tends to be insufficient.
  • the method of compounding the composition comprising the inorganic layered compound and the biodegradable high hydrogen bonding resin is not particularly limited.
  • a mixed solution of a solution in which a biodegradable high hydrogen bonding resin is dissolved and a dispersion in which the inorganic layered compound has been swollen and cleaved in advance, and the solvent is removed; a dispersion in which the inorganic layered compound has been swollen and cleaved is produced.
  • Any of the following methods can be used: a method in which the solvent is added to the degradable high hydrogen bonding resin and the solvent is removed; and a method in which the biodegradable high hydrogen bonding resin and the inorganic layered compound are heat-kneaded.
  • the former two methods are preferably used from the viewpoint that a large aspect ratio of the inorganic layered compound can be easily obtained.
  • the laminated form or molded form of the resin composition of the present invention comprises a biodegradable resin and a biodegradable resin composition containing an inorganic layered compound having an aspect ratio of 50 or more and 500 or less.
  • a part or layer
  • any form such as a film, a sheet, and a container can be used.
  • the base material a part or a part other than the layer composed of the resin composition of the present invention
  • the resin composition of the present invention is used as a laminate is also required. It is preferably made of a biodegradable material (biodegradable resin, paper, wood, etc.).
  • the biodegradable resin film in this embodiment comprises a layer 1 of a biodegradable resin composition containing an inorganic layered compound.
  • the biodegradable resin film of the present invention may have a laminated structure as shown in the schematic sectional view of FIG. 5 or FIG.
  • the biodegradable resin film in the embodiment shown in FIG. 5 is obtained by disposing a layer 1 of a biodegradable resin composition containing an inorganic layered compound on a substrate composed of a biodegradable resin layer 2.
  • the biodegradable resin film in the embodiment of FIG. 6 is obtained by disposing a layer 1 of a biodegradable resin composition containing an inorganic layered compound on a substrate composed of a biodegradable resin layer 2.
  • a biodegradable resin layer 2a is further disposed thereon.
  • the method of laminating the above-mentioned resin composition of the present invention on a substrate is not particularly limited.
  • a coating method of applying a coating solution to the surface of a substrate film, drying and heat-treating is preferably used. More specifically, such coating methods include gravure methods such as a direct gravure method, a reverse gravure method, and a microgravure method; rolls such as a two-hole single-beat coat method, a bottom feed method and a three-reverse coat method. Coating method; Doc Yuichi knife method, die coating method, dip coating method, bar coating method, a coating method combining these, and the like.
  • the thickness of the coating film (the thickness of the layer composed of the resin composition of the present invention) varies depending on the type of the base material and the desired barrier performance, but is preferably 10 zm or less in dry thickness, and higher transparency is required. If the dry thickness is less than 2 zm (especially less than 1 m) More preferred.
  • the lower limit of the coating thickness is not particularly limited, but is preferably 1 nm or more, more preferably 1 Onm or more (especially 100 nm or more), from the viewpoint of obtaining a sufficient gas barrier effect.
  • additives such as an ultraviolet absorber, a coloring agent, and an antioxidant may be mixed into the resin composition, the film or the molded product of the present invention as needed, as long as the effects of the present invention are not impaired. Or may be added. Further, it is needless to say that an adhesive and a printing ink at the time of lamination can be used as needed.
  • cultivation soil Korean Taihei Horticulture cultivation soil, manufactured by Taihei Bussan: nitrogen 0.35 g / l kg, phosphoric acid 1.5 g / l kg, potassium 0.35 gZl kg, pH 6. 0 ⁇ 6. 5
  • thickness of about 150 ⁇ M three film samples of the bottom area of approximately 28. 4 cm 2, not overlapping arrangement on the soil as did.
  • the above-mentioned sample film was further covered with the above-mentioned cultivation medium to fill a 100 OmL polycup.
  • Residual area ratio (film bottom area after decomposition test) / (film bottom area before decomposition test) x 100
  • the measurement was performed according to the method (JISK-7126) specified in Japanese Industrial Standards (JIS).
  • test piece a sample film (test piece) was attached to a commercially available oxygen permeability measuring device (trade name: OX-TRAN 10/50 A, manufactured by MOCON, USA), and the temperature was 31 ° C.
  • OX-TRAN 10/50 A oxygen permeability measuring device
  • the thickness of 0.5 mm or more was measured with a commercially available digital thickness gauge (contact thickness gauge, trade name: Ultra-high precision deci-micro head MH-15M, manufactured by Nippon Kogaku Co., Ltd.).
  • a thickness of less than 0.5 m can be determined by gravimetric analysis (the measured weight of a film of a certain area is divided by the area and then by the specific gravity of the composition) or elemental analysis (biodegradable resin composition). (In the case of a laminate of a product and a substrate).
  • the laminate is identified as inorganic. From the ratio between the elemental analysis value (derived from the composition layer) and the specific element (for example, Si) fraction of the inorganic layered compound alone, the ratio of the layer composed of the resin composition of the present invention to the base material was calculated. I asked more.
  • a commercially available ultrafine particle size analyzer (trade name: BI-90, manufactured by Brookhaven, USA, Japan agent: Nikkiso Co., Ltd.)
  • the center diameter obtained from the photon correlation method by the dynamic light scattering method (The output) was taken as the particle size.
  • the measured data of the particle size of each standard sample was within the range of 10% by a calibration measurement using the following standard sample of true spherical fine particles. I went while confirming that.
  • Natural montmorillonite (trade name Kunipia F; manufactured by Kunimine Kogyo Co., Ltd.) is dispersed in ion-exchanged water (electric conductivity: 0.7 S / cm or less) to a concentration of 2 wt. This was used as a layered compound dispersion (solution A).
  • the particle size of the montmorillonite was 560 nm, the unit thickness a value obtained from powder X-ray analysis was 1.2156 ⁇ m, and the aspect ratio was 461.
  • polyvinyl alcohol (trade name? 1171 ⁇ ; manufactured by Kuraray Co., Ltd., saponification degree: 99.6%, polymerization degree 1700) becomes 2 wt.% In ion-exchanged water (0.7 zS / cm or less). This was used as a resin solution (solution B).
  • a corona-treated poly-3-hydroxybutyrate (trade name “PAIOPOL 0% HV” manufactured by ICI) having a thickness of 150 ⁇ m was used as a substrate film, and the above composition was coated on the substrate film. The solution was applied, dried at room temperature, and further dried at 80 ° C for 2 hours to obtain a laminated film. The dry thickness of the coating layer was 0.5 im.
  • the oxygen permeability of the laminated film at 31 ° C. and 61% RH (relative humidity) was 0.09 cc / m 2 ⁇ day ⁇ atm, and was excellent in gas barrier properties.
  • a laminated film was prepared in the same manner as in Example 1 except that the configuration shown in Table 1 was adopted, and an oxygen permeability test and a biodegradability test of the film were performed. The results obtained from these tests are shown in Table 1 below.
  • di-ruconium carbonate ammonium As a crosslinking agent for hydrogen-bonding groups, di-ruconium carbonate ammonium
  • a laminated film was prepared in the same manner as in Example 1 except that the configuration shown in Table 1 was adopted, and the film was subjected to an oxygen permeability test and a biodegradability test. The results obtained from these tests are shown in Table 1 below.
  • the laminated film obtained in this example was excellent in both gas barrier properties and biodegradability.
  • zirconium carbonate ammonium manufactured by Daiichi Rare Element Co., Ltd., trade name: zircosol AC7, aqueous solution containing 15 wt.% In terms of zirconium oxide
  • polyvinyl alcohol The mixture was added to the mixed solution of the solution A / solution B prepared in Example 1 so that the ratio of 1 mol of the zirconium element to 15 mol of the hydroxyl group was adjusted.
  • the layers were laminated in the same manner as in Example 1. After forming the film, the laminated film was heat-treated at 140 ° C. for 10 minutes using a hot air drier.
  • a film was prepared in the same manner as in Examples 1 to 3, except that the layer comprising the resin composition of the inorganic layered compound / biodegradable resin was not provided, and an oxygen permeability test and a biodegradability test of the film were performed. Was done. Table 1 shows the obtained results.
  • a film was prepared in the same manner as in Examples 1 to 3 except that the inorganic layered compound dispersion liquid (solution A) used in Example 1 was not used, and an oxygen permeability test and a biodegradability test of the film were performed.
  • Table 1 shows the obtained results.
  • PHB Poly-3-hydroxybutyrate (made by ICI: trade name Biopol HV0%)
  • HBHV4 3-hydroxybutyrate (96%) —3-hydroxyperylene (4%) copolymer (made by ICI: trade name Biopol HV 4%)
  • HBHV9 3-hydroxybutyrate (91%) — 3-hydroxyperylene —G (9%) copolymer (manufactured by ICI: product name Biopol HV9%)
  • LDPE Low-density polyethylene film (Sumitomo Chemical Co., Ltd., trade name: Sumikasen F 208-C molded at 180 ° C)
  • Z Zirconium carbonate ammonium aqueous solution (manufactured by Dai-ichi Rare Element Industry, trade name: zirconazole AC7)
  • FIG. 8 is a graph showing the X-ray diffraction peak of the polyvinyl alcohol PVA-1I7H / Kunipia F composition used in the above example
  • FIG. 9 is the Kunipia F (montmorillonite) used in the above example.
  • 3 is a graph showing an X-ray diffraction peak of the sample.
  • a good gas can be obtained while substantially maintaining biodegradability.
  • a resin composition, film or molded article having barrier properties can be obtained.
  • the resin composition of the present invention may be in the form of a film, for packaging foods such as frozen foods such as miso, bonito, confectionery, ramen, ham, sausage, retort foods, croquettes, etc. It is preferably used for packaging and the like. It is also preferably used as a molded product such as a bottle and a tray for squeeze bottles of mayonnaise, juice, soy sauce, edible oil, sauces, microwave food trays, and cups of yogurt. Since the resin composition of the present invention can exhibit good biodegradability when used in any of the above-mentioned forms, it can treat garbage or plastic waste, reduce landfill garbage, etc. Can greatly contribute to the preservation of the global environment.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne une composition de résine biodégradable comprenant une résine biodégradable ainsi qu'un composé inorganique en couches présentant un rapport d'élancement compris entre 50 et 5.000, ainsi qu'un film et un moulage présentant chacun une couche (1) dont au moins une partie comprend la composition précitée. Ladite composition, ledit film et ledit moulage présentent de bonnes propriétés de barrage aux gaz tout en conservant sensiblement la biodégradabilité de la résine, et par conséquent ils contribuent considérablement à la protection de l'environnement tel que lors de la mise au rebut de détritus et de déchets en plastique, et par la réduction de la quantité de déchets destinés à des décharges.
PCT/JP1995/000071 1994-01-24 1995-01-24 Composition, film et moulage de resine biodegradable WO1995020013A1 (fr)

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US08/522,423 US6146750A (en) 1994-01-24 1995-01-24 Bio-degradable resin composition, film and shaped article
EP95906506A EP0691381A4 (fr) 1994-01-24 1995-01-24 Composition, film et moulage de resine biodegradable

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JP6/006013 1994-01-24
JP601394 1994-01-24

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US6573340B1 (en) 2000-08-23 2003-06-03 Biotec Biologische Naturverpackungen Gmbh & Co. Kg Biodegradable polymer films and sheets suitable for use as laminate coatings as well as wraps and other packaging materials
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JP6331652B2 (ja) * 2014-04-25 2018-05-30 凸版印刷株式会社 ガスバリア性フィルムおよびガスバリア性積層体
CN111303468B (zh) * 2020-04-22 2022-03-01 泰山学院 一种营养型可降解地膜材料的制备方法

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CA2158944A1 (fr) 1995-07-27
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EP0691381A4 (fr) 1996-07-17

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